Styrene, alpha methyl styrene, drying oil fatty acid interpolymers



Patented May 19, 1953 2,639,272 .1 131;. ALPHA METHYL STYEN gemidcertain new interp s ogy 1 arri Tneiriifritinals bemin-staf'mtnudcof'making the interpoiymers. VIt i's"lgiownthat'varnish resinsmay be prepareci by interpoiymeratinof "dryingoiis with However;atterpiais" made'to "carrst is" y fm-- asstarting finan-135 A, Grriewss`and Arthur S. Teot, Midland,

Application April28, 1 9, Serial No.T 6

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inatic orrrpoun'd:n nterpoiymerizei; therewith.AThe"poiymer-ii'cproducts are all soluble in toluene and irange fromvAclear toiuerie-soluhle `tiroducts thrcnigl'i'i- '1c1oi1dy; tof opaquelinterpolyrners, foetending inparwpon medew-ee of. ueeiurlafol i. e. thenumber of o'ienic linkages 'in the "oi'i fattyfacifstarting materiaia Yl Th'evfa'ctttha'tthe'fnt'erpolymer is clouiyfor Qaaquefnot @myindicatesfthatfthe'relative 9129- vioitioris ofthe drying-oil fatty acidandthe inigt're "jcnsistin lof as monovinyl aromatic cornflvpound an'the alpha#methylenel alkyl" f aromatic compound; is approximatelythefcritical proportioiiswfo'ri the' @preparation offciear-'pol`ymer ic.i'oducts in accordance -Witlra '-prerferre farao-=ti`co|f"`thenvention;but 'also indicatesi-thatfthe number'of"foiennie-fimkagesy ire: the degreeA of hnsatuiationyof thdryingoilfatty ad'fs ap- ,proxirnatelythe minimum Value required for theAf1jria'rtio' f'iclear*interpoiymersrom the mix- 3 ture of polymerizablecomponents in those relative proportions. In some instances, therefore,the polymeric products may be cloudy to opaque, throughout a part, orparts, of the complete range of proportions, particularly when an oilfatty acid, e. g. soybean oil fatty acids, which contains an averagenumber of olefinic linkages corresponding to an iodine number of about130, or less, is employed as the polymerizable oil fatty acid componentof the mixture of polymerizable starting materials. However, the opaquecompositions are useful in the preparation of enamels, i. e. varnishesto which pigments are added, and in the manufacture of iloor covering,e. g. linoleum. The clear interpolymers are useful in the `preparationof varnishes, e. g. by cooking the same with drying oils, or byesterication of the carboxylic acid groups with monoand polyhydriealcohols such as butanol, glycerine, or pentaerythritol, etc. Certain ofthe clear interpolymers are also useful in the preparation of modifledalkyd resins, particularly those containing about 70 per cent by Weightor less of the mixture consisting of a monovinyl aromatic compound, e.g. styrene, and an alpha-methylene alkyl aromatic compound, preferablyalphamethyl styrene, chemically combined, i. e. interpolymerized, withthe drying oil fatty acid. The modified alkyd resins may be prepared byesterifying the carboxylic acid groups in the interpolymer with apolyhydric alcohol such as `glycerine or pentaerythritol so as to form aproduct containing free hydroxyl groups and thereafter reacting theproduct with phthalic acid or phthalic anhydride.

Any drying oil fatty acid, or mixture of drying oil fatty acidscontaining conjugated or nonconjugated olenic linkages, which drying oilfatty acid is free of functional groups other than the carboxylic acidgroup, may be employed in preparing the new interpolymers. Examples ofsuitable drying oil fatty acids are linseed oil fatty acids, soybean oilfatty acids, hempseed oil fatty acids, dehydrated castor oil fattyacids, tung oil fatty acids, perilla oil fatty acids, or i'lsh oil fattyacids such as sardine oil fatty acids or menhaden oil fatty acids, etc.Mixtures of any two or more of such drying `oil fatty acids may also beused. The drying oil fatty acids are prepared by saponication of thecorresponding drying oils and may be purchased in commercial quantities.

As the monovinyl aromatic compound starting material, styrene ispreferred but other polymerizable nuclear substituted alkyl styrenessuch as ortho-methyl styrene, para-methyl styrene, ortho-ethyl styrene,para-ethyl styrene, ortho,- para-dimethyl styrene, ortho,paradiethylstyrene, ortho-methyl-para-isopropyl styrene, or ortho-methyl-para-ethylstyrene, etc., may be employed.

Alpha-methyl styrene is preferably used as the alpha-methylene alkylaromatic component of the compositions. However, other alpha-methylenealkyl aromatic compounds such as alphaethyl styrene,para-methyl-alpha-methyl styrene, ortho,paradimethyl-alpha-methylstyrene. ortho,paradiethyl-alpha-methyl styrene, paraethyl-alpha-methylstyrene, para-isoprcpyl-alpha-methyl styrene, or ortho,paradiisopropylalpha-methyl styrene, etc., may be. employed. Mixtures of any of thesecompounds with one another, or with alpha-methyl styrene may also beused.

In preparing interpolymersof the drying Vcil fatty acid, or a mixture ofthe rdrying oil fatty acids, and a mixture consisting of a monovinylaromatic compound and an alpha-methylene alkyl aromatic compound, thealpha-methylene alkyl aromatic compound, e. g. alpha-methyl styrene, maybe used in amount corresponding to from 15 to 50, preferably from 20 to40, per cent by weight of the combined weight of the alpha-methylenealkyl aromatic compound and the monovinyl aromatic compound, preferablystyrene. The drying oil fatty acid, or mixture of drying oil fattyacids, may be used in amount corresponding to from 10 to 90 per cent byweight of the combined Weight of the polymerizable materials, themixture consisting of a monovinyl aromatic compound and thealpha-methylene alkyl aromatic compound making up the remaining to l0per cent by Weight of said polymerizable materials to a total of percent.l

The polymerizable starting materials are preferably polymerized in aclosed container, or in contact with an inert atmosphere, e. g.nitrogen, helium, or methane, etc., in the absence of an inert liquidmedia such as benzene, toluene, or xylene, etc. However, thepolymerization may be carried out with limited access of air, e.g. byWay of a reflux condenser, to the materials. In practice, the drying oilfatty acid, the monovinyl aromatic compound, and the alpha-methylenealkyl aromatic compound, are mixed together in the desired proportionsand the mixture is heated at a temperature below its atmospheric boilingpoint until polymerization is substantially complete. The polymerizationmay be carried out at temperatures of from to 300 C., but temperaturesof from to200 C. are preferred. The mixture should not be heated to atemperature suiiicient to cause decomposition of the product.Polymerization is usually complete after 10 to 50 hours of heating atthe pref erred temperatures.

The rate of polymerization may be increased by adding to the vstartingmixture a small amount, e. g. from 0.5 to 3 per cent by weight, of apolymerization catalyst :such as benzoyl peroxide, acetyl benzoylperoxide, tertiary-butyl perbenzoate, or .tertiary-,butyl hydroperoxide,etc. The addition of a' polymerization catalyst is advantageous in thatit permits the production of clear interpolymers employing the dryingoil fatty acid and the mixture consisting ofr a monovinyl aromaticcompound, e. g. styrene, and 'the alphamethylene alkyl aromaticcompound, preferably alpha-methyl styrene, in a somewhat wider range ofproportions than can be used in the absence of a catalyst.

In preparing certain of the interpolymers, particularly those in which adrying oil fatty acid having a low degree of unsaturation, e. g. soybeanoil fatty acids, or hempseed oil fatty acids, is employed, the clarity,i. e. the tendency of the polymeric product to be opaque, is materiallyaffected by the manner in which the ingredients are mixed together. Bestresults are frequently obtained when the drying oil fatty'acid, or themixture of drying oil fatty acids, is first heated to a polymerizationtemperature and a mixture of the monovinyl aromatic compound, e. g.styrene, the alpha-methylene alkyl aromatic compound, e. g. alpha-methylstyrene, and a polymerization catalyst is added over a period of severalhours.

Upon completion of the polymerization reaction, volatile ingredients, e.g. unreacted styrene or alpha-methyl styrene, may be separated from thepolymeric product by heating the mixture in vacuum toa temperature ofabout 200 C., or by other, uouat et sa ty. dtilatilt. 9% volatile..ingrediente @t atmoh.. by. laussingv steam temnemtur-.e suieieht to.oeue. @esp moratorium;

@wir-.1g illu @te @ottico @t .Praet .e gettone.;

uw fPoxymeric @529ML im was interpolymerzed in adm 'L and alpha-methylAstyrene. in each of a series of @fi .lled y ,ym welght'of eachcomponent,

at a tempearture of about 200 C. was then passed through the reactionmixture for a period of three hours to distill Volatile ingredients. Themixture was thereafter heated at temperatures between 170 and 200-C.,under an absolute pressure of about 380 mm. of Hg for a period of 0.6hour, then cooled to room temperature. A total of 6.75 pounds of oil wasseparated from the reaction mixture. The product consisted of 131 poundsof a clear solid resin having a melting point of 118 F., an acid numberof 52.2 and contained 0.64 per cent by weight of volatile material. Asolution consisting of 60 per cent by weight of the resin in toluene hada viscosity of R-S 4(Gardner-I-Ioldt scale) EXAMPLE 6 By proceduresimilar to that described in Example 5, a resin was prepared from amixture consisting of 24 pounds of tung oil fatty acid, 27.2 pounds ofalpha-methyl styrene, 108.8 pounds of styrene and 1.6 pounds of benzoylperoxide as polymerization catalyst. The product was a clear amber resinhaving a melting point of 150 F. A solution consisting of 60 per cent byweight of the resin in toluene had a viscosity of W-X (Gardner Holdt).

EXAMPLE 7 A chargeconsisting of 28.2 pounds of dehydrated castor oilfatty acids was placed in a reaction vessel. The mixture was stirred andheated to a temperature of 140 C. Thereafter, a mixture consisting of103.5 pounds of styrene, 25.1 pounds of alpha-methyl styrene and 1.6pounds of benzoyl peroxide as polymerization catalyst was added to thedehydrated castor oi-l fatty acid over a period of 4 hours. Theternperature of the mixture was then gradually raised to 200 C. over aperiod lof 4 hours, and was maintained at a temperature of 200 C. vfor12 hours longer. Volatile ingredients were then separated from thereaction mixture by procedure similar to that described in Example 5. Atotal of 4.5 pounds of oil was separated from the reaction mixture. Theproduct consisted of 138 pounds of a clear resin having a melting pointof 130 F., an acid number of 38.1, and contained 1.01 per cent volatilematter. A solution consisting of 60 per cent by weight of the resin intoluene had a viscosity of T (Gardner-Holdt).

EXAMPLE- 8 EXAMPLE 9 A charge consisting of 60 grams of linseed oilfatty acid was placed in a reaction ask equipped with a reflux condenserand stirrer. The mixture was stirred and heated to a. temperature of 140C. Thereafter, a mixture consisting of 192 grams of styrene, 48 grams ofalphamethyl styrene and 3 grams of benzoyl peroxide as polymerizationcatalyst, was added to the heated linseed oil fatty acid over a periodof 4 hours. The vtemperatureof themixture was then grad- 8. ually raisedto 200 C. over a period of 5 hours as refluxing permitted and wasmaintained at a temperature of 200 C., for 13 hours longer. Steam wasthen passed through the reaction mixture at a temperature of 200 C. fora time of 30 minutes to distill volatile ingredients. There# after, themixture was heated at temperatures between 160 and 200 C. under anabsolute pressure of about 6 mm. of Hg for a time of 3 hours, thencooled to room temperature. The product Was a clear resin having amelting point of F., and contained 0.31 per cent by Weight of volatilematerial. A solution consisting of 60 per cent by Weight of the resin intoluene had a viscosity of M-N (Gardner-Holdt).

EXAMPLE 10 By procedure similar to that described in Example 9, a resinwas prepared by interpolymerizing a mixture consisting of 42.75 grams oftung oil fatty acid and 14.25'grams of linseed oil fatty acid, with amixture consisting of 192 grams of styrene and 48 grams of alpha-methylstyrene, which latter mixture contained 3 grams of benzoyl peroxide aspolymerization catalyst. The product was a clear amber resin having amelting point of 120 F. A solution consisting of 60 per cent by weightofthe resin in toluene had a viscosity of RS (Gardner-Holdt).

EXAMPLE 11 A mixture consisting of 14.25 grams of tung oil fatty acidand 42.75 grams of dehydrated castor oil fatty acid was interpolymerizedwith a mixture consisting of 48 grams of alpha-methyl styrene and 192grams of styrene, which latter mixture contained 3 grams of benzoylperoxide as polymerization catalyst, by procedure similar to thatdescribed in Example 9. The product was a clear amber colored resinhaving a melting point of F. A solution consisting of 60 per cent byweight of the resin in toluene had a viscosity of T-U (Gardner-Holdt).

Other modes of applying the principle of the invention may be employedinstead of those explained, change being made as regards the method orproducts herein disclosed, provided the steps or substances stated byany of the following claims or the equivalent of such stated steps orsubstances be employed.

We claim:

1. A process for making a toluene-soluble in#v terpolymer of a monovinylaromatic compound, an alpha-methylene alkyl aromatic compound and adrying oil fatty acid, which comprises interpolymerizing from 10 to 90parts by weight of a drying oil fatty acid and from 90 to 10 parts of amixture consisting of from 50 to 85 per cent by weight of a monovinylaromatic compound having the formula: v

and from 50 to 15 per cent of an alpha-methylene alkyl aromatic compoundhaving the formula:

R @das in which formulas X and Y each represents a member of the groupconsisting of hydrogen and lower alkyl radicals containing not more than9 three carbon atoms and R is an alkyl radical containing not more thantwo carbon atoms, by

heating the mixture of polymerizable materials' terpolymer of styrene,alpha-methyl styrene and a drying oil fatty acid, which comprisesinterpolymerizing a mixture consisting of from 10 to 90 parts by weightof a drying oil fatty acid and from 90 to 10 parts of a mixtureconsistingnor from 50 to 85 per cent by weight of styrene land from 50to 15 per cent of alpha-methyl styrene'g;

by heating the mixture at temperatures between 120 and 300 C.

4. A1toluenesolub1e interpolymer composed-lof(- from 10 to 90 parts byweight of a dryng'joill fatty acid and from 90 to 10 parts of amixture21.,A

consisting of from 50 to 85 per cent by weight ofl a monovinyl aromaticcompound having the formula:

@was

and from 50 to 15 per cent of an alpha-methylene alkyl aromatic compoundhaving the formula:

10 ln which formulas X and Y each represents a member of the groupconsisting of hydrogen and lower alkyl radicals containing not more thanthree carbon atoms and R is an alkyl radical containing not more thantwo carbon atoms.

5. A toluene-soluble interpolymer as claimed in claim 4 wherein thedrying oil fatty acid is tung oil fatty acid.

6. A toluene-soluble interpolymer as claimed in claim 4 wherein thedrying oil fatty acid is linseed oil fatty acid.

7. A toluene-soluble interpolymer as claimed in claim 4 wherein thedrying oil fatty acid is a mixture consisting of tung oil fatty acid andsoybean oil fatty acid.

8. A toluene-soluble nterpolymer composed of a drying oil fatty acid,styrene and alpha-methyl styrene in substantially the proportions:drying oil fatty acid from 10 to 90 parts by weight, and a mixtureconsisting of styrene and alpha-methyl styrene to 10 parts by weight, inwhich mixture the alpha-methyl styrene is from 15 to 50 per cent byweight of the combined weight of the alpha-methyl styrene and thestyrene.

GERALD A. GRIESS. ARTHUR S. TEOT.

References Cited in the le of this patent UNITED STATES PATENTS NumberName Date 2,190,915 Bass et al. Feb. 20, 1940 2,320,724 Gerhart et al.June 1, 1943 2,457,768 Arvin et al. Dec. 28, 1948 2,468,748 Griess etal. May 3, 1949 2,468,770 Morris et al. May 3, 1949 2,470,757 BobaleckMay 24, 1949 2,560,592 Opp et al. July 17, 1951

1. A PROCESS FOR MAKING A TOLUENE-SOLUBLE INTERPOLYMER OF A MONOVINYLAROMATIC COMPOUND, AN ALPHA-METHYLENE ALKYL AROMATIC COMPOUND AND ADRYING OIL FATTY ACID, WHICH COMPRISES INTERPOLYMERIZING FROM 10 TO 90PARTS BY WEIGHT OF A DRYING OIL FATTY ACID AND FROM 90 TO 10 PARTS OF AMIXTURE CONSISTING OF FROM 50 TO 85 PER CENT BY WEIGHT OF A MONOVINYLAROMATIC COMPOUND HAVING THE FORMULA: